• Journal of the Korean Chemical Society
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• v.36 no.2
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• pp.318-323
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• 1992

Following seven new nucleophilic adducts of sulfilimine compounds were prepared by the addition of 1-methyl-5-mercapto-1,2,3,4-tetrazole to vinylsulfilimine derivatives; S-Phenyl-S-2-(1-methyl-1,2,3,4-tetrazole-5-thio)-ethyl-N-p-tosylsulfilimine, S-p-tolyl-S-2-(1-methyl-1,2,3,4-tetrazole-5-thio)-ethyl-N-p-tosylsulfilimine, S-m-tolyl-S-2-(1-methyl-1,2,3,4-tetrazole-5-thio)-ethyl-N-p-tosylsulfilimine, S-p-chlorophenyl-S-2-(1-methyl-1,2,3,4-tetrazole-5-thio)-ethyl-N-p-tosylsulfilimine, S-p-bromophenyl-S-2-(1-methyl-1,2,3,4-tetrazole-5-thio)-ethyl-N-p-tosylsulfilimine, S-p-methoxyphenyl-S-2-(1-methyl-1,2,3,4-tetrazole-5-thio)-ethyl-N-p-tosylsulfilimine and S-p-nitrophenyl-S-2-(1-methyl-1,2,3,4-tetrazole-5-thio)-ethyl-N-p-tosylsulfilimine. The structures of these adducts were confirmed by elemental analyses, MP, UV, IR-and NMR-Spectra.

• Journal of the Korean Chemical Society
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• v.18 no.6
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• pp.423-429
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• 1974

The rate constant of the addition of hydrogen cyanide to $ ${\alpha}$-cyano-\beta-piperonylacrylic$ acid (CPA) were determined by UV spectrophotometry at various pH and a rate equation which can be applied over wide pH range was obtained. From this equation, one may conclude that below pH 3 the reaction is started by the addition of hydrogen cyanide molecule to CPA, however, at pH 6~8, hydrogen cyanide is added to $ {\alpha}$-cyano-$ {\beta}$-piperonyl acrylate anion. From pH 3 to 6, these two reaction are competitive. Above pH 9, the reaction is proceeded by the addition of cyanide ion to $ {\alpha}$-cyano-$ {\beta}$-piperonyl acrylate ion. From pH 3 to 9, the complex reaction mechanism can also be fully explained by the rate equation obtained.

• Journal of the Korean Chemical Society
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• v.39 no.8
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• pp.650-656
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• 1995

Rate Constants of hydrolysis of N-(benzenesulfonyl)-C-(N-methylanilino)imidoyl chlorides were determined by UV spectrophotometry in 50% (v/v) aqueous methanol at 25$^{\circ}C.$ On the basis of rate equation, substituent effect, solvent effect, salt effect, thermodynamic parameters and hydrolysis product analysis, it may be concluded that the hydrolysis of N-(benzenesulfonyl)-C-(N-methylanilino)imidoyl chlorides proceed through $S_N1$ mechanism via azocarbonium ion intermediate below pH 9.0, while aebove pH 10.0 the hydrolysis proceeds through nucleophilic addition-elimination ($Ad_{N-E}$) mechanism.

• Bulletin of the Korean Chemical Society
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• v.26 no.5
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• pp.776-780
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• 2005

The kinetic studies of the reactions of $\alpha$-chloroacetanilides $(YC_6H_4NRC(=O)CH_2Cl;\;R=H\;(4)\;and\;CH_3$ (5)) with pyridines have been carried out in dimethyl sulfoxide at 95 ${^{\circ}C}$. The pyridinolysis rates are faster with 4 than with 5 whereas the aminolysis rates with benzylamines are faster with 5 than with 4. The Brønsted ${\beta}_X$ values are in the range from 0.30 to 0.32 and the cross-interaction constants, $\rho_{XY}$, are small negative values; $\rho_{XY}$ = -0.06 and -0.10 for 4 and 5, respectively. Based on these and other results, the pyridinolyses of $\alpha$-chloroacetanilides are proposed to proceed via a stepwise mechanism with rate-limiting addition of the nucleophile to the carbonyl group to form zwitterionic tetrahedral intermediate ($T^{\pm}$) followed by a bridged type transition state to expel the leaving group.

• Bulletin of the Korean Chemical Society
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• v.34 no.7
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• pp.1985-1989
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• 2013

A simple colorimetric and fluorescent anion sensor 1 based on salicylimine showed a high selectivity and sensitivity for detection of cyanide in aqueous solution. The receptor 1 showed high selectivity toward $CN^-$ ions in a 1:1 stoichiometric manner, which induces a fast color change from colorless to orange and a dramatic enhancement in fluorescence intensity selectively for cyanide anions over other anions. Such selectivity resulted from the nucleophilic addition of $CN^-$ to the carbon atom of an electron-deficient imine group. The sensitivity of the fluorescence-based assay (0.06 ${\mu}M$) is below the 1.9 ${\mu}M$ suggested by the World Health Organization (WHO) as the maximum allowable cyanide concentration in drinking water, capable of being a practical system for the monitoring of $CN^-$ concentrations in aqueous samples.

• Reproductive and Developmental Biology
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• v.33 no.1
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• pp.1-5
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• 2009

To search a new pig pheromonal odorant, the $N^1$-allyl-$N^2$-(tetrahydrofuran-Z-ylmethyl)oxalamide molecule predicted by ligand based approach and molecular docking method was synthesized by nucleophilic addition-elimination reaction ($Ad_{NU-E}$) between N-allyloxalamic acid ethylester and tetrahydrofurlmethylamine. According to the evaluation results for efficiency of pig estrus control, the synthesized pig pheromonal $N^1$-allyl-$N^2$-(tetrahydrofuran-2-ylmethyl)oxalamide molecule advanced the estrus by 11.3 days (p<0.05) compared with the non-pheromone group. And from these results, it is predicted that the synthesized pig pheromonal compound will be able to increase the reproduction efficiency of pig.

• Bulletin of the Korean Chemical Society
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• v.24 no.2
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• pp.205-208
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• 2003

Laser-induced Raman spectroscopy has been utilized to demonstrate its feasibility for studying the kinetics of imine formation in chloroform solvent. The imine formation, by the nucleophilic addition of primary amine to the carbonyl group of ketone, has been monitored at ten minute intervals for eight hours. The intensity of the C=O stretching mode at 1684 $cm^{-1}$ was measured to determine the rate constant of the reaction. In order to correct the sample-to-sample fluctuations in Raman peak area, this peak was normalized to the C-Cl bending peak at 666 $cm^{-1}$. By the peak area change during the course of reaction, the second order rates at three different temperatures have been determined. The substituent effects on the π conjugations of imine product have also been investigated. On the basis of Raman frequency shifts, the delocalization properties of the aromatic system modified by substitution of a hydrogen atom with -Cl and $-CH_3O$ groups could be clearly understood.

• Bulletin of the Korean Chemical Society
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• v.35 no.8
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• pp.2381-2384
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• 2014

A solid-phase synthetic approach is reported for the synthesis of an ascorbic acid (ASA)-dipeptide conjugate that exhibited enhanced antioxidant activity. The N-terminal amino group of dipeptide (Ala-Ala) on a resin support was first activated by 1,1'-carbonyldiimidazole (CDI), and then reacted with an ASA derivative. The addition of a base, triethylamine (TEA), promoted nucleophilic acylation of ASA derivative and yielded a desired product (ASA-Ala-Ala) with enhanced purity, when cleaved from the resin. Compared to the approach where a C3 hydroxyl group of ASA was first activated with CDI and then reacted with the amino group of dipeptide on the resin, this new approach allowed a significant reduction of a total reaction time from 120 h to 8 h at $25^{\circ}C$. As-prepared ASA-dipeptide conjugate (ASA-Ala-Ala) showed improved antioxidant activity compared to ASA.

• Applied Chemistry for Engineering
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• v.3 no.1
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• pp.100-110
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• 1992

Arylsulfonyl urea derivatives can be easily prepared in good yield by treating amines with arylsulfonyl carbamates in aqueous solution : 1) N-Arylsulfonyl-N'-aryl urea derivatives, 2) N-Arylsulfony-N'-alkyl urea derivatives, 3) N-Arylsulfonyl-N'- heterocyclic urea derivatives. The proposed reaction mechanisms for preparing arylsulfonyl ureas involve formation of an ion-pair conformation by initial acid-base reaction, then formation of a so-called tetrahedral intermediate by nucleophilic addition, followed by an acid-catalyzed elimination of an alkoxide ion and loss of a proton.

• Natural Product Sciences
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• v.12 no.4
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• pp.175-192
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• 2006

Screening for the cytotoxicity from plant origin is the first stage for anti-cancer drug development. A variety of terpenoids with exomethylene, epoxide, allyl, $\alpha,\beta-unsaturated$ carbonyl, acetylenes, and $\alpha-methylene-\gamma-lactone$ induces apoptosis and/or differentiation as well as cytotoxicity through the ROS signal transduction pathways. These are found among monoterpenes, sesquiterpenes, triterpenes, flavonoids, coumarins, diarylheptanoids, and even organosulfuric compounds. The most essential characteristics of natural cytotoxic substances is to possess the strong electrophilicity that is susceptible to nucleophilic biomolecules in the cell. Thiol-reductants and superoxide dismutase can block or delay apoptosis. Thus, ROS and the resulting cellular redox-potential changes can be parts of the signal transduction pathway during apoptosis. Disturbance of the balance of oxireduction by the pigment of natural quinones also caused the induction of the differentiation and apoptosis. Saponins with the cytotoxicity are restricted to their monodesmosides, rather than to bisdesmosides. Those saponins exhibited calcium ion-mediated apoptosis in addition to cytotoxicity whereas they showed also differentiation without extracellular calcium ion. The properties on cytotoxicity, apoptosis, and differentiation were assumed to depend on resultant oxidative stress to the cells. In this review, we describe a spectrum of cytotoxic compounds with various action mechanisms.